Tracking flowpaths in a complex karst system through tracer test and hydrogeochemical monitoring: Implications for groundwater protection (Gran Sasso, Italy).

Groundwater in karst aquifers is frequently tapped for drinking purposes, due to frequent huge volumes of resources. Unfortunately, vulnerability of these aquifers can be high, due to possible fast transfer of recharge water on springs by the karst network. On Gran Sasso Mountain regional aquifer, several springs are subjected to drinking withdrawal and an updated evaluation of their potential is now a fundamental issue to be considered, facing climate change effects, which reflect on variation of discharge regimen and values. To distinguish between different contribution of spring recharge, a tracer test has been carried out on the Vitella d'Oro spring, fed both by the regional aquifer and by a local system exposed to karst features developed in the Rigopiano Conglomerates formation. Thanks to hydrogeological, hydrogeochemical and isotopic data, a conceptual model of spring recharge has been proposed and subsequently validated by the tracer test results. All information confirms the superimposition on the regional base flow, by a relevant contribution of the karst network, influencing the spring discharge in recharge periods. In detail, a fast flow component is responsible for discharge peaks and frequently of turbidity events, having a mean velocity ranging from 30 to 70 m/h in the aquifer. Besides of this fast flow, an additional aliquot of the recharge is due to the same local aquifer, but slower flow clearly identifiable by hydrochemistry and isotopic data. Thanks to these findings, a renewed management of the spring has been suggested, considering the different degrees of aquifer vulnerability (turbidity occurrence) directly related to the discharge regimen.

Partial nitrification enhances natural attenuation of nitrogen in a septic system plume.

Natural attenuation of nitrogen (N) was investigated in a well characterized septic system plume at a campground in Ontario, Canada. Total inorganic N (TIN) concentrations in deeper portions of the plume were about one third of the septic tank value of 40.7mgL-1. NH4+ and NO3- isotopic characterization were used to provide insight into potential attenuation processes. Concentrations of NH4+ and NO3- were highly variable in the plume, but approached the septic tank TIN value in some shallow zones and exhibited δ15N values like the tank value of +6‰. However, isotopic enrichment (up to +24‰ for NH4+ and +45‰ for NO3-) and declining TIN concentrations in the deeper zones indicated that anaerobic ammonium oxidation contributed to the TIN attenuation. The degree of isotopic enrichment increased at lower NH4+ concentrations and was consistent with Rayleigh-type distillation with an enrichment factor (Ɛ) of -5.1‰. Additionally, decreasing DOC values with depth and the concomitant enrichment of δ15NNO3 and δ18ONO3, suggested that denitrification was also active. The N attenuation observed in the Killarney plume was partly due to incomplete nitrification that occurred because of the shallow water table, which varied from only 0.2-0.7m below the tile bed infiltration pipes. Moreover, some of the monitoring locations with the shallowest water table distances from the infiltration pipes, had the highest degree of TIN attenuation (70-90%) in the plume. This behavior suggests that controlling water table distance from the infiltration pipes could be a useful mechanism for enhancing N attenuation in septic system plumes.

Occurrence of volatile organic compounds in shallow alluvial aquifers of a Mediterranean region: Baseline scenario and ecological implications.

A regional survey of eight volatile organic compounds (VOCs), namely BTEX (benzene, toluene, ethylbenzene and p-xylene) and four chlorinated aliphatic hydrocarbons (CAHs: chloroform, 1,2-dichloroethane, trichloroethene and tetrachloroethene), was carried out at 174 sites, in 17 alluvial aquifers of Abruzzo, a Mediterranean region of southern Italy, from 2004 to 2009. Frequency of detection, concentration range, spatial distribution pattern, and temporal trend of contaminant concentration in each aquifer were analyzed as well as the relationships between VOC concentrations and the total amount of precipitation during the 90days preceding each sampling date. A review of published ecotoxicological data, providing an indication of the biological risk associated with the observed levels of VOC contamination, was presented and discussed. BTEX concentrations were under detection limits in all the investigated aquifers, indicating absence of contamination. In contrast, CAH contamination occurred in 14 out of 17 aquifers. The two most frequently detected compounds were chloroform and tetrachloroethene. No significant temporal trend was observed for chloroform and tetrachloroethene concentrations during the six years of observation, indicating the persistence of stable contaminations, except for some slightly decreasing trends observed in three out of 17 aquifers. In four aquifers chloroform and tetrachloroethene concentrations increased with precipitations in the preceding months. Spatial patterns of contamination differed among aquifers, indicating highly complex contaminant distributions at aquifer scale not related to single-plume geometries. Patterns of contamination by chloroform and tetrachloroethene in the most urbanized aquifers were likely associated with multiple sources of VOCs not clearly detectable at the scale used in this study. In five out of 17 aquifers, chloroform and tetrachloroethene co-occurred at concentrations that are lethal to groundwater-dwelling organisms under a short exposure period (four days). Future studies should therefore consider the possibility that in the other aquifers groundwater-dwelling organisms might be physiologically damaged by sublethal VOC concentrations.

Fate of arsenic, phosphate and ammonium plumes in a coastal aquifer affected by saltwater intrusion.

A severe groundwater contamination with extensive plumes of arsenic, phosphate and ammonium was found in a coastal aquifer beneath a former fertilizer production plant. The implementation of an active groundwater remediation strategy, based on a comprehensive pump and treat scheme, now prevents the migration of the dissolved contaminants into the marine environment. However, due to the site's proximity to the coastline, a seawater wedge was induced by the pumping scheme. Additionally the groundwater flow and salinity patterns were also strongly affected by leakage from the site's sewer system and from a seawater-fed cooling canal. The objective of this study was to elucidate the fate of arsenic and its co-contaminants over the site's history under the complex, coupled hydrodynamic and geochemical conditions that prevail at the site. A detailed geochemical characterisation of samples from sediment cores and hydrochemical data provided valuable high-resolution information. The obtained data were used to develop various conceptual models and to constrain the development and calibration of a reactive transport model. The reactive transport simulations were performed for a sub-domain (two-dimensional transect) of an earlier developed three-dimensional flow and variable density solute transport model. The results suggest that in the upper sub-oxic zone the influx of oxygenated water promoted As attenuation via co-precipitation with Al and Fe oxides and copper hydroxides. In contrast, in the deeper aquifer zone, iron reduction, associated with the release of adsorbed As and the dissolution of As bearing phases, provided and still provides to date a persistent source for groundwater pollution. The presented monitoring and modelling approach could be broadly applied to coastal polluted sites by complex contaminant mixture containing As.

Performance of different assessment methods to evaluate contaminant sources and fate in a coastal aquifer.

The present study deals with the application of different monitoring techniques and numerical models to characterize coastal aquifers affected by multiple sources of contamination. Specifically, equivalent freshwater heads in 243 monitoring wells were used to reconstruct the piezometric map of the studied aquifer; flow meter tests were carried out to infer vertical groundwater fluxes at selected wells; deuterium and oxygen isotopes were used to identify the groundwater origin, and tritium was analyzed to estimate the residence time; compound-specific isotope analyses and microbial analyses were employed to track different sources of contamination and their degradation; numerical modelling was used to estimate and verify groundwater flow direction and magnitude throughout the aquifer. The comparison of the information level for each technique allowed determining which of the applied approaches showed the best results to locate the possible sources and better understanding of the fate of the contaminants. This study reports a detailed site characterization process and outcomes for a coastal industrial site, where a comprehensive conceptual model of pollution and seawater intrusion has been built using different assessment methods. Information and results from this study encourages combining different methods for the design and implementation of the monitoring activities in real-life coastal contaminated sites in order to develop an appropriate strategy for control and remediation of the contamination.

Reactive modelling of 1,2-DCA and DOC near the shoreline.

1,2-Dichloroethane (1,2-DCA) was found to be the most abundant compound among chlorinated hydrocarbons detected in a petrochemical plant in southern Italy. This site is located near the coastline, and it is set above an unconfined coastal aquifer, where seawater intrusion is present. The presence of organic and inorganic contaminants at this site has required the implementation of remediation strategies, consisting of pumping wells (hydraulic barrier) and a horizontal flow barrier. The purpose of this work was to assess the influence of salt water intrusion on the degradation rate of 1,2-DCA. This was done on a three-dimensional domain relative to a limited portion of a well characterized field site, accounting for density-dependent flow and reactive transport modelling of 1,2-DCA and Dissolved Organic Carbon (DOC). The modelling procedure was performed employing SEAWAT-4.0 and PHT3D, to reproduce the complex three-dimensional flow and transport domain. In order to determine the fate of 1,2-DCA, detailed field investigations provided intensive depth profile information. Different, kinetically controlled degradation rates were simulated to explain the observed, selective degradation of pollutants in groundwater. Calibration of the model was accomplished by comparison with the two different sets of measurements obtained from the MLS devices and from pumping wells. With the calibrated model, it was possible to distinguish between dispersive non-reactive processes and bacterially mediated reactions. In the non-reactive model, 1,2-DCA sorption was simulated using linear sorption coefficient determined with field data and 1,2-DCA degradation was simulated using a first order decay coefficient using literature data as initial guess. Finally, on the reactive transport model, where a two-step approach with partial equilibrium approach was implemented, the effects of neglecting the cation exchange capacity, omitting density-dependent flow, and refining the vertical discretization of the model were investigated. Comparison of results from various scenarios shows that geochemical changes in inorganic constituents can be used to improve the site's conceptual model, and establishes that natural degradation processes can be suitable for 1,2-DCA as a remediation option.